Steady-State Kinetics of α-Synuclein Ferrireductase Activity Identifies the Catalytically Competent Species

Biochemistry. 2017 May 16;56(19):2497-2505. doi: 10.1021/acs.biochem.7b00257. Epub 2017 May 4.

Abstract

α-Synuclein (α-syn) is a cytosolic protein known for its association with neurodegenerative diseases, including Parkinson's disease and other synucleinopathies. The potential cellular function of α-synuclein may be of consequence for understanding the pathogenesis of such diseases. Previous work has suggested that α-synuclein can catalyze the reduction of iron as a ferrireductase. We performed a detailed analysis of the steady-state kinetics of recombinant α-syn ferrireductase activity and for disease-associated variants. Our study illustrates that the ferrireductase activity we observed is clearly commensurate with bona fide enzyme activity and suggests a mechanistic rationale for the activity and the relationship to cellular regulation of the pool of Fe(III) and Fe(II). Using cell-based studies, we examined the functionally active conformation and found that the major catalytically active form is a putative membrane-associated tetramer. Using an artificial membrane environment with recombinant protein, we demonstrate that secondary structure folding of α-synuclein is insufficient to allow enzyme activity and the absolute specificity of the tertiary/quaternary structure is the primary requirement. Finally, we explored the steady-state kinetics of a range of disease α-synuclein variants and found that variants involved in neurodegenerative disease exhibited major changes in their enzymatic activity. We discuss these data in the context of a potential disease-associated mechanism for aberrant α-synuclein ferrireductase activity.

Publication types

  • Comparative Study
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acid Substitution
  • Binding Sites
  • Biocatalysis
  • Cell Line, Tumor
  • FMN Reductase / chemistry
  • FMN Reductase / genetics
  • FMN Reductase / metabolism*
  • Humans
  • Liposomes
  • Membrane Proteins / chemistry
  • Membrane Proteins / genetics
  • Membrane Proteins / metabolism*
  • Models, Biological*
  • Molecular Weight
  • Mutation
  • Nanostructures / chemistry
  • Nerve Tissue Proteins / chemistry
  • Nerve Tissue Proteins / genetics
  • Nerve Tissue Proteins / metabolism*
  • Neurons / enzymology*
  • Neurons / metabolism
  • Recombinant Proteins / chemistry
  • Recombinant Proteins / metabolism
  • Solubility
  • Substrate Specificity
  • alpha-Synuclein / chemistry
  • alpha-Synuclein / genetics
  • alpha-Synuclein / metabolism*

Substances

  • Liposomes
  • Membrane Proteins
  • Nerve Tissue Proteins
  • Recombinant Proteins
  • alpha-Synuclein
  • FMN Reductase
  • ferric citrate iron reductase